JP2002506118A - Thermal reaction products from maleic anhydride and oligoalkenes, derivatives of thermal reaction products with amines or alcohols and uses thereof - Google Patents

Abstract

(57) Abstract: Linearization by metallocene catalysis in the presence of maleic anhydride and a titanium, zirconium or hafnium metallocene catalyst and an activator based on organoaluminum, organoboron or carbocationic compounds obtained by oligomerization of C ₈ -C _{12-1-alkenes,} thermal reaction products from oligo alkene having a number average molecular weight of a and 700-20000 vinylidene double bond components above 30%. The invention furthermore relates to derivatives thereof with amines or alcohols and their use as fuel and lubricant additives.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a thermal reaction product of maleic anhydride and an oligoalkene comprising a specific linear α-olefin and having a number average molecular weight of 700 to 20,000, and a method for producing the thermal reaction product About. Furthermore, the present invention relates to derivatives of the thermal reaction products with amines or alcohols in the form of the corresponding alkenylsuccinamides, alkenylsuccinimides or alkenylsuccinates, and to the derivatives as fuel and lubricant additives. About use. The subject of the present invention is also a motor oil containing this derivative as an additive.

As ashless dispersants in the form of alkenylsuccinic acid derivatives, imides of polyisobutenylsuccinic acid have hitherto been known. This polyisobutenyl group and the corresponding other long-chain groups known from the prior art do not yet take into account the optimum characteristic spectrum of such dispersants. In particular, the viscosity properties still need to be improved, ie a lowering of the low temperature viscosity is desirable.

[0003] WO-A 93/24539 (1) shows that from C ₃ -C ₂₀ -1-olefins, for example propene, 1-butene, 1-pentene or 1 hexene, the number-average molecular weight 30
Poly-1-olefins having from 0 to 10000 are known and are produced by conventional metallocene catalysis. Said 1-olefins are always used in a mixture with readily volatile saturated or unsaturated hydrocarbons, for example industrial butane / butene
Streams or industrial isobutene-containing butene streams (Raffinate I / II from steam crackers) are used. The poly-1-olefin obtained is then converted to a product functionalized with maleic anhydride, which is used in particular for lubricating oils and as a fuel additive.

WO-A 96/28486 (2) is based on metallocene-catalyzed processes from unsaturated dicarboxylic acids or their anhydrides and oligomers of 1-olefins having 3 to 14 C atoms. And a copolymer of As 1-olefin, n-decene is particularly mentioned. The average molecular weight of this olefin oligomer is 3
00 to 10000. It is suitable as a fuel additive and a lubricant additive after a copolymer obtained from an unsaturated dicarboxylic acid (anhydride) and an olefin oligomer is derivatized with an amine.

[0005] WO-A 96/23751 (3) discloses olefin oligomers prepared using metallocene catalyst systems, which are linear and cyclic C ₂ -C ₁₂ -olefins, such as 1-decene Based on The weight average molecular weight ( _Mw ) is 100 to 20,000 in a molecular weight distribution _Mw / _Mn (weight average / number average) of 1.0 to 2.4. Its degree of polymerization is in the range from 2 to 200. The olefin oligomer can be further processed to a functionalized compound according to (3) using conventional chemical reactions, such as hydroformylation and / or hydroamination, which can be a fuel additive or a lubricant. Suitable as an additive.

It was an object of the present invention to overcome the disadvantages of the prior art.

[0007] Accordingly, the vinylidene double bond component obtained by oligomerization of maleic acid with a linear C ₈ -C ₁₂ -1-alkene is obtained in an amount of more than 30%, preferably more than 50%, in particular more than 60% And a thermal reaction product from an oligoalkene having a number average molecular weight of 700 to 20,000.

[0008] linear C ₈ -C _12-1-alkenes and 1-octene as a mixture, 1-nonene, 1-decene, 1-undecene and 1-dodecene and mixtures thereof. In a preferred embodiment, it is obtained by metallocene-catalyzed oligomerization of linear 1-decene, whereby 40 mol%, based on the amount of linear 1-decene, is obtained.
Other linear C ₈ -C _12-1-alkene is built polymerization (einpolymerisieren) which may be oligo alkene is used to.

The essential monomer component in this preferred embodiment is therefore linear 1-decene, alone or up to 40 mol%, preferably 20 mol%, based on the amount of 1-decene up, in particular other linear C ₈ to 5 mol% -C _12-1-alkene (1-O punctuation, 1-nonene, 1-undecene and / or 1-dodecene) be oligomerized in admixture with it can.

The 1-alkene is in chemically pure form (usually purity of 99 to 99.9% by weight).
Or as an industrial mixture, usually with a purity of 90-99% by weight,
In the case of industrial mixtures, the remaining components are usually polymerizable or non-polymerizable components of approximately the same volatility (eg unsaturated isomers, analogs or saturated hydrocarbons)
It is in the form of In general, the 1-alkenes used are practically free of volatile components, in particular free of volatile saturated or unsaturated hydrocarbons, in particular those having less than 8 C atoms, The term "free" means that the proportion of such volatile components is at most less than 1% by mass, especially less than 0.5% by mass.

In the case of the oligomerization of the abovementioned linear C ₈ -C ₁₂ -1-alkenes, metallocene catalysis is advantageous, in particular titanium-, zirconium- or hafnium-metallocene catalysts and organoaluminum compounds, organoboron compounds or It works in the presence of activators based on carbocationic compounds.

The system of metallocene-catalyst and activator used for this oligomerization is
It is a normal catalyst system. Variations in the metallocene structure can adjust the desired molecular weight range of the oligoalkene, as is known. The oligomerization is generally carried out in a suitable medium (reaction mixture), for example an organic solvent, under the conditions customary for this purpose.

There are no special requirements for the catalyst system, but it is necessary that the catalyst system be sufficiently soluble in the reaction mixture. The reaction mixture is the mixture that is present from the time when all the reaction components are brought together to the time after the oligomer reaction has decomposed the catalyst system. The solubility of the catalyst system in the reaction mixture is determined by measuring the turbidity of the reaction mixture similar to DIN 38404. If the turbidity is in the range from 1 to 10, preferably in the range from 1 to 3, the catalyst system is sufficiently soluble.

The metallocene component of the catalyst system is a complex of titanium and zirconium hafnium, where the metal atom M is sandwiched between two optionally substituted cyclopentadienyl groups, In this case, the remaining valences of the central atom M are saturated with easily exchangeable leaving atoms or leaving groups X ¹ and X ² .

Suitable metallocene complexes are those of the general formula: Cp ₂ MX ¹ X ^{2 wherein} M represents titanium, zirconium or hafnium, preferably zirconium.

Cp ₂ is a pair of optionally substituted cyclopentadienyl-ligands. In this case, both cyclopentadienyl-ligands may be substituted only one or both.

When the substituent represents a C ₅ -C ₃₀ alkyl group, the cyclopentadienyl is usually symmetrically substituted. This means that the type, number and position of the alkyl substituent on one Cp ring correspond to the type, number and position of the alkyl substituent on the second Cp ring. The number of alkyl groups per cyclopentadienyl ring is 1 to 4
Individual.

Suitable C ₅ -C ₃₀ alkyl groups are aliphatic groups, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl and These isomers are, for example, neopentyl, isooctyl, and the cycloaliphatic radicals cyclopentyl and cyclohexyl. Particularly suitable is n-octadecyl.

The optional C ₅ -C ₃₀ alkyl-substituted cyclopentadienyl units may be substituted by one to two C ₄ -C ₁₀ alkyl units each, which together with the cyclopentadienyl unit To form a fused ring system, for example, a tetrahydroindenyl system.

Substituted cyclopentadienyl-ligands also include pairs in which at least one cyclopentadienyl unit is substituted with at least one organosilyl group —Si (R ¹ ) ₃ . R ¹ is a C ₁ -C ₃₀ carbon-organic group, for example,
Methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-
Butyl, t-butyl, n-pentyl, i-pentyl, neopentyl, hexyl,
Represents heptyl, octyl, nonyl, cyclohexyl, phenyl or p-tolyl. Preferred organosilyl groups are trimethylsilyl and t-butyldimethylsilyl,
Particularly, trimethylsilyl.

For the case of the organosilyl substituent on the cyclopentadienyl unit, a contrasting substitution model is not absolutely necessary, nor is it excluded.

Of interest are also metallocene catalysts in which both cyclopentadienyl-ligands are linked to one another via a bridging member. Such bridge members are usually 1 to
4 atoms (C atoms and / or heteroatoms such as Si, N, P, O, S, Se
Or B) and optionally alkyl side chains, for example 1,2-ethylidene, 1,3-propylidene or dialkylsilane-bridges.

The general formula Cp ^₂ MX ¹ X ₂ of the possible easy replacement of the metallocene complexes, the following can be listed as formally leaving atom or a leaving group X ^1, X ² negative load electricity: hydrogen , Halogens such as fluorine, bromine, iodine and preferably chlorine. In addition:
Alcoholates such as methanolates, ethanolates, n- and i-propanolates, phenolates, trifluoromethylphenolates, naphtholates and silanolates.

Furthermore, for X ¹ and X ² , especially aliphatic C ₁ -C ₁₀ alkyl groups, especially methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, neopentyl, hexyl, preferably methyl, t- butyl and neopentyl, further cycloaliphatic C ₃ -C ₁₂ hydrocarbon group, such as cyclopropyl, Shikurobuchi Le, cyclopentyl and especially cyclohexyl or C ₅ -C ₂₀ bicycloalkyl, for example Bishikuropenchiru and in particular bicycloheptyl And bicyclooctyl are recommended.

The substituents X ¹ , X ² having aromatic structural units include: C ₆ -C ₁₅ aryl, preferably phenyl or naphthyl, each having from 1 to 10 C atoms in the alkyl radical. And alkylaryl or arylalkyl having 6 to 20 C atoms in the aryl group, for example tolyl and benzyl.

Detailed examples of suitable metallocene complexes are: bis (n-octadecylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl)) zirconium dichloride, bis (tetrahydroindenyl) zirconium dichloride, bis [( t-butyldimethylsilyl) cyclopentadienyl] -zirconium dichloride, bis (di-t-butylcyclopentadienyl) zirconium dichloride, (ethylidene-bisindenyl) -zirconium dichloride,
[Ethylidene-bis (tetrahydroindenyl)] zirconium dichloride and bis [3,3 (2-methyl-benzindenyl)] dimethylsilanediyl-zirconium dichloride.

Suitable metallocene complexes are readily known in the art, for example, Brauer (Hrsg.): Handbuch d.
er Praeparativen Anorganischnen Chemie, Band 2, 3rd edition, Page 1395-1397
, Enke, Stuttgart 1978. An advantageous method starts from the corresponding substituted lithium salt of cyclopentadienyl, which is reacted with a transition metal halide.

Although it is advantageous to use one metallocene complex in the oligomerization reaction, it is also possible to use a mixture of different metallocene complexes.

In addition to the metallocene complex, the catalyst system also contains an activator, which is known per se and is referred to in the literature as a cocatalyst. Generally, this involves alkylating the transition metal component of the catalyst system and / or abstracting ligand X from the transition metal component,
Eventually, a catalyst system for the oligomerization of the olefinically unsaturated hydrocarbon can be formed. For this task, organometallic compounds of the first to third main groups or the second subgroup of the periodic table are generally suitable, but other acceptor compounds, for example carbocation salts, can also be used.

Activator compounds which are particularly suitable in the context of the invention are, in addition to aluminum fluoride, in particular organoaluminum and organoboron compounds and carbocationic salts. Advantageously, open-chain or cyclic oligomeric aluminoxane compounds (Alumoxanverbindungen)
), Which can be obtained by the reaction of aluminum trialkylene, in particular trimethyl- or triethylaluminum, with water.

Suitable cocatalysts are also generally aluminum organos of the general formula Al (R ² ) ₃ , wherein R ² is hydrogen, C ₁ -C ₁₀ alkyl, preferably C ₁ -C ₄ alkyl, Especially methyl, ethyl or butyl. Furthermore R ² has 1 to 10 C atoms in the alkyl group, and may be in the aryl group is an aryl alkyl or alkyl aryl having 6 to 20 C atoms.

Furthermore, R ² has, in addition to the radicals defined above, fluorine, chlorine, bromine or iodine, provided that at least one R ² is a C-organic group or an aluminum alkyl Al (R ² ₃ ) is suitable. Particularly preferred compounds are trimethylaluminum, triethylaluminum, triisobutylaluminum, di-isobutylaluminum hydride and diethylaluminum chloride.

In addition, organic boron compounds such as tris-arylboron compounds, preferably tris (pentafluorophenyl) boron, and also salts of carbonium ions, preferably triphenylmethyltetraarylborate, especially triphenylmethyltetra, are used as activators. (Pentafluorophenyl) borate is also suitable.

The above Al-, B- or C-compound is known and can be obtained by a method known per se.

The activators can be used in the catalyst system alone or as a mixture.

The activator component is preferably used in a molar excess relative to the metallocene complex. The molar ratio of activator to metallocene complex is generally from 100: 1 to 10,000: 1, preferably from 100: 1.
: 1 to 1000: 1.

The components of the catalyst system described above can be introduced into the oligomerization reactor individually or as a mixture in any order. The metallocene complex is advantageously mixed with the at least one activator component before it is introduced into the reactor, ie is advantageously preactivated.

The production of oligoalkenes can be carried out intermittently or, preferably, continuously in a reactor usually used for the oligomerization of olefins. Suitable reactors are, in particular, continuously operated stirred vessels, in which case a series of a plurality of series-connected stirred vessels can also be used.

This oligomerization reaction can be carried out in a suspension, a liquid monomer and an inert solvent. In the case of the oligomerization reaction in a solvent, use is made in particular of liquid organic hydrocarbons, for example benzene, ethylbenzene or toluene. The oligomerization reaction is preferably carried out in a reaction mixture in which the liquid monomer is present in excess.

The oligomerization is generally carried out between -20 ° C. and 200 ° C., preferably between 0 ° C. and 140 ° C., in particular between 3 ° C.
Since it is carried out at a temperature between 0 ° C. and 110 ° C., this oligomerization can usually be carried out by low-pressure or medium-pressure methods. The amount of catalyst used is not critical.

Oligoalkenes prepared with metallocene catalysts contain unsaturated double bonds due to their oligomerization mechanism, in which case the proportion of terminal vinylidene-double bonds is particularly high, which indicates that maleic anhydride and Allows a sufficiently complete thermal reaction of

The oligoalkenes described are from 700 to 20,000, preferably from 1000 to 18000
, In particular 2,000 to 15,000, more in particular having a number average molecular weight of 3,000 to 12,000 and (M _n). The measurement of the number average molecular weight is usually performed by gel permeation chromatography (GPC).

The molecular weight distribution M _w / M _n (weight-average / number-average) is generally between 1.5 and 5, where a narrow distribution is produced, for example, by a method of extracting a wider distribution of the sample, Obtained by mixing. If a single catalyst system is used, this distribution will generally be between 1.8 and
3.0. In some cases, a wider distribution is more advantageous, but especially a broad low molecular weight cross-section in the distribution improves the dispersing effect of the final product. Furthermore, the bimodal distribution obtained by mixing also has a beneficial effect.

The oligoalkenes described include maleic anhydride (MSA) and the usual thermal “En”-
The reaction converts to alkenyl succinic anhydride, which generally comprises one alkenyl chain.
Each has 1-2 succinic anhydride units. For this reason, maleic anhydride and oligoalkenes are advantageously reduced to 150-150 in the absence of compounds which cause radical chain reactions.
Heat to 250 ° C, preferably 170-220 ° C. The reaction is advantageously carried out with an inert gas (
(E.g., nitrogen).

The thermal reaction products from maleic anhydride and oligoalkenes according to the invention are converted to the corresponding alkenyl succinamides, -imides or -esters in the customary manner with amines or alcohols, such derivatives Are also an object of the present invention.

In this case, as the alcohol, a polyol, in particular, an aliphatic polyhydroxy compound having 2 to 6 hydroxyl groups is used. Examples of diols are ethylene glycol, 1,2- and 1,3-dihydroxypropane, dihydroxybutane and dihydroxypentane. Examples of triols are glycerin, trihydroxybutane, trihydroxypentane and trimethylolpropane. Examples of higher alcohols are pentaerythritol, mannitol and sorbitol.

To form the corresponding succinimide or succinamide derivative, at least one secondary amine function (NH) or a primary amine function (
NH ₂ ). Of particular interest here are linear or branched alkylene polyamines, cycloaliphatic polyamines and heterocyclic polyamines, each having from 2 to 6 amino groups. Examples for this are ethylene polyamines such as ethylene diamine, diethylene triamine, triethylene tetraamine, tetraethylene pentaamine or pentaethylene hexaamine, propylene polyamine, dimethylaminopropylamine, α, β-diaminopropane, α, β-diaminobutane, Di (trimethylene) triamine, butylene polyamine, piperazine or diaminocyclohexane.

Of particular interest as derivatives of the thermal reaction product from maleic anhydride and oligoalkenes according to the invention are the corresponding alkenyl succinimides, which are derived from polyamines having at least one primary amino function. Be guided.

A preferred embodiment is such a derivative in the form of the corresponding alkenyl succinimide of the thermal reaction product from maleic anhydride and an oligoalkene with an amine, the derivative comprising maleic anhydride and an oligoalkene. And the polyamine used, the amount of polyamine used exceeds the theoretical amine requirement for the preparation of bissuccinimide by 10 to 200% and the condensation thus obtained is obtained. The amine value of the product is at least 70% of the theoretically calculated amine value of bissuccinimide, based on the saponification value of the reaction product from maleic anhydride and the oligoalkene.

In the maleation of the oligoalkene (typical conditions: 4 h, 200 ° C., 10% by weight of MSA with respect to the oligoalkene), after the MSA has been distilled off and the alkenylsuccinic anhydride has been filtered off, the acid or saponification value ( Obviously another reaction which does not provide VZ) proceeds and a subsequent imidization step with polyamine (typical conditions: 3h, 180
℃) and reacts with amine groups while losing basicity (amine value).

The theoretical amine value is calculated from the saponification value of alkenyl succinic anhydride (SA) under the assumption of an imidization reaction between 2 mol of anhydride and 1 mol of polyamine (eg, tetraethylenepentamine, TEPA). Is done. In the case of using a theoretical amount of amine, a theoretical amine value is not obtained and a bad dispersing effect occurs. The more the amine value deviates from the theoretical value, the worse this dispersion effect becomes. The amount of amine was increased at least to the extent that a theoretical amine number was achieved during the condensation. In this regard, an excellent dispersion effect was obtained.

As regards the amount of amine used, a distinctly higher amine number results for bissuccinimides. The repetition finally achieved an amount of amine corresponding to three of the original five amino functions after condensation in the case of TEPA. The optimum effect is usually between the two end points (Eckpunkten).

Two examples illustrate the unexpected difference between alkenyl succinic anhydride and amine requirements in Table 1 below:

[0054]

[Table 1]

The derivatives according to the invention of the thermal reaction products of maleic anhydride and oligomers with amines or alcohols are useful as fuel additives and in particular as lubricant additives
In particular, it is particularly excellent and suitable as an ash-free dispersant in motor oil. The derivatives according to the invention exhibit excellent viscosity-temperature properties in the motor oils added thereby, so that the use of conventional viscosity index-improvers can be fully or at least partially omitted. In particular, a distinct reduction in low-temperature viscosity is achieved. further,
This derivative already shows excellent dispersing effects in small amounts.

The subject of the present invention is that from 0.1 to 10% by weight, especially from 0.5 to 10% by weight, according to the invention, of the thermal reaction products of maleic anhydride and oligoalkenes with amines or alcohols, based on motor oil. It is also a motor oil containing 7% by mass. Motor oils are defined herein as mineral substances and partially or fully synthesized motor oils (eg mineral oils, synthetic components such as organic esters, synthetic hydrocarbons, poly-α-
Motor oils based on olefins or polyolefins, for example polyisobutene or mixtures with synthetic components such as mineral oil beds). Such a coater oil can be used for various purposes (for example, four-cycle engine oil, two-cycle engine oil, automobile motor oil, motorcycle motor oil, marine diesel motor oil, locomotive diesel motor oil, etc.). The derivatives according to the invention of the thermal reaction products are also suitable as additives in gear oils.

The following examples further illustrate the invention but do not limit the invention. Percentages always relate to mass, unless otherwise stated.

PREPARATION EXAMPLES Example 1: Synthesis of oligodecene with M _n = 11400 400 ml of linear 1-decene (polymer quality, 99.8%) were placed in a 1 liter stirred autoclave with a double jacket of V4A-steel. Charged together with 300 ml of dry ethylbenzene using Al ₂ O ₃ and heated to 500 ° C. In a shaking vessel (Schlenkgefaess), 44 mg of (ethylidene-bisindenyl) zirconium dichloride were added to 43.8 ml of methylaluminoxane (10 in n-hexane).
%), Pressurized into the reactor in small increments with nitrogen through a gate, and postwashed with 30 ml of ethylbenzene. The supply was distributed so that the cryostat for removing the reaction heat did not become overloaded and the reaction temperature could be maintained at 50 ° C. A temperature difference between the jacket of the maximum of 40 ° C. and the inside of the reactor occurs, and this temperature difference is 2-3
Solved as time progressed. After 4 hours, cool to room temperature, open the autoclave and dilute with an aliquot of cyclohexane. Wash twice with 100 ml of 0.1% sulfuric acid and twice with 100 ml of demineralized water, dry over Na ₂ SO ₄ and at 225 ° C. (2 mbar
) Until complete distillation. The bottoms had a viscosity of 1100 mm ² / s (100 ° C.) and a _Mn of 11400 by GPC. The yield was 85% and the vinylidene double bond content was 94%.

Example 2: Reaction of the oligodecene from Example 1 with maleic anhydride (MSA) and derivatization with tetraethylenepentamine (TEPA) 200 g of the oligodecene from Example 1 together with 20 g of MSA, consisting of V2A-steel 0
. It was charged into a 5 liter stirred autoclave, evacuated to 20 mbar, depressurized with nitrogen and evacuated again to 20 mbar. It was then heated to 200 ° C. and maintained for 4 hours, after which the pressure was released and the excess MSA was removed at 2 mbar. The reaction product had a saponification value of 6.0. After lowering the temperature to 180 ° C., TEPA1.
53 g were added and condensation was carried out after 2 hours. The imide has an acid value of 0.7 and an amine value of 4.8.
Met.

Example 3 Synthesis of Oligodecene with M _n = 5600 Using 400 ml of linear 1-decene (purity: 96%) and Al ₂ O ₃ in a 1 l stirred autoclave with double jacket according to example 1. 300 ml of dry ethylbenzene was charged and cooled to 0 ° C. In a shaking vessel, 80 mg of bis (n-octadecylcyclopentadienyl) zirconium dichloride were activated with 32 ml of methylaluminoxane (10% in n-hexane) and added twice every 5 minutes. A temporary temperature increase of 2-3 ° C. was observed. After 8 hours at 0 ° C., the reactor was opened and the reaction was stopped by slow dropwise addition of dilute sulfuric acid with stirring and worked up as in Example 1. An oligodecene having a viscosity of 580 mm ² / s at 100 ° C. and a GP _n of 5600 was obtained. The yield was 83% and the vinylidene double bond content was 95%.

Comparative Example A Derivative of polyisobutenyl succinic anhydride (PIBSA) with TEPA For comparison, a high reactivity with a number average molecular weight (M _n ) of 2330 and a vinylidene double bond content of 77% 200 g of polyisobutene is made of V2A-steel.
Charged into a 5 liter stirred autoclave, heated to 160 ° C., evacuated and stripped with nitrogen. While stirring, 13 g of MSA in liquid form were fed during 1 hour. Subsequently, the mixture was heated to 225 ° C. and reacted for 4 hours. Excess MSA was removed under 2 mbar vacuum. The reaction product had a saponification value of 42. After the temperature had dropped to 180 ° C., TEPA was added in a ratio of 1: 2 to PIBSA, ie 7.9 g, and condensation was carried out after 2 hours.

Testing of Viscosity-Temperature-Properties The product from Example 2 and Comparative Example A were tested as a ashless dispersant at a concentration of 6% in a 5W / 30 motor oil having the following composition:

Normal poly-α-olefin (viscosity: 6 mm ² / s) 54.4 or 48.4% Normal poly-α-olefin (viscosity: 4 mm ² / s) 20% Diisononyl adipate 20% Ash-free Dispersant 0 or 6% normal overbased sulfonate 3% zinc dithiophosphate 1.8% normal antioxidant 0.5% normal friction modifier 0.2% normal antifoam 0.1% The results are summarized in Table 2:

[0064]

[Table 2]

The dispersants according to the invention from Example 2 clearly outperform the prior art (Comparative Example A) because of the higher viscosity-increasing action at high temperatures, and at the same time the low viscosity at low temperatures.

Test for dispersing action For the test for dispersing action, the spot test (Les Huiles pour Moteurs et la Graissag
e des Moteurs, A. Schilling, Vol. 1, p. 89f, 1962). For this, a 3% mixture of the dispersant in diesel oil was produced. The dispersant thus obtained was developed on a filter paper like chromatography. The rating scale is from 0 to 1000; the higher the value obtained, the better the dispersing action.

The results are summarized in Table 3:

[0068]

[Table 3]

The dispersants according to the invention from Example 2 show in all cases a significantly improved dispersing action than the prior art, with 2% of the product from Example 2 already having 3% of Comparative Example A
The dispersing action equivalent to the dispersing action using was achieved.

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] January 11, 2000 (2000.1.11)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10M 133/56 C10M 133/56 145/16 145/16 149/06 149/06 // C10N 20:02 C10N 20:02 20:04 20:04 30:04 30:04 40:25 40:25 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AU, BG, BR, BY, CA, CN , CZ, GE, HU, ID, IL, IN, JP, KR, KZ, LT, LV, MK, MX, NO, NZ, PL, RO, RU, SG, SI, SK, TR, UA, USF Terms (reference) 4H013 CD00 4H104 BC 09C BF03C CB09C CE03C EA03C LA02 PA41 4J100 AA15Q AK32P CA04 CA31 DA01 FA10 HA45 HA55 HA61 HC09 HC10 HC43 HC46

Claims (10)

[Claims] 1. A with maleic anhydride, obtained by oligo mers of linear C ₈ -C _{12-1-alkenes,} have a vinylidene double bond components above 30% and 700
Thermal reaction products from oligoalkenes having a number average molecular weight of ２０20,000. 2. Obtained by oligomerization by metallocene catalysis in the presence of a titanium metallocene catalyst, a zirconium metallocene catalyst or a hafnium metallocene catalyst and in the presence of an activator based on an organoaluminum compound, an organoboron compound or a carbocation compound. The thermal reaction product of claim 1 from an oligoalkene. 3. A obtained by oligomerization of linear 1-decene, whereby the linear up to 40 mol% relative to the amount of 1-decene other linear C ₈ -C _12-1-alkene co 3. A thermal reaction product according to claim 1 or 2 from an oligoalkene which may be incorporated. 4. Oligoalkenes obtained by oligomerization of 1-alkenes which are used without volatile hydrocarbons which actually have less than 8 C atoms,
A thermal reaction product according to any one of claims 1 to 3. 5. The thermal reaction product according to claim 1, wherein the product is an oligoalkene having a number average molecular weight of 2,000 to 15,000. 6. The method according to claim 1, wherein the maleic anhydride and the oligoalkene are heated to a temperature of from 150 to 250 ° C. in the absence of a compound causing a radical chain reaction.
The method for producing a thermal reaction product according to any one of the preceding claims. 7. The corresponding alkenylsuccinamide, alkenylsuccinimide or alkenyl of the thermal reaction product of maleic anhydride and oligoalkene according to claim 1 with an amine or alcohol. Derivatives in the form of succinates. 8. A polyamine which is obtained by condensation of the reaction product of maleic anhydride and an oligoalkene with a polyamine, wherein the amount of polyamine used is less than 10 theoretical amine requirements for the preparation of bissuccinimide. And the amine number of the condensate thus obtained is at least 70% of the theoretically calculated amine number of bissuccinimide relative to the saponification number of the reaction product of maleic anhydride and oligoalkene. 8. A derivative of the corresponding alkenyl succinimide of the thermal reaction product of maleic anhydride and an oligoalkene with an amine according to claim 7, wherein the amine is: 9. An amine or alcohol according to claim 7 or 8 as a fuel and lubricant additive, in particular as an ashless dispersant in motor oil.
Use of derivatives of thermal reaction products from maleic anhydride and oligoalkenes. 10. A motor containing from 0.1 to 10% by mass, based on a motor oil, of a derivative of a thermal reaction product of maleic anhydride and an oligoalkene with an amine or an alcohol, according to claim 7 or 8. oil.